Quaternary ammonium salts of acetylenenic carboxylic acids



Unimd States Paten 3,340,265 QUATERNARY AMMONIUM SALTS F ACETYLENIC CARBOXYLIC ACIDS Reginald L. Wakeman, Philadelphia, Pa., and E. Griflin Shay, Belle Mead, N.J., assignors, by mesne assignments, to Millmaster Onyx Corporation, New York, N.Y., a corporation of New York No Drawing. Filed Apr. 23, 1964, Ser. No. 362,559

7 Claims. (Cl. 260-286) The object of the present invention is the preparation of relatively water-insoluble, microbiologically active compounds by reaction of certain quaternary ammonium hydroxides or their water-soluble salts with acetylenic carboxylic acids or their water-soluble salts.

The products of this invention conform, in general, to the following structure:

wherein Z is the cation of a microbiologically active qua ternary ammonium compound; R is the residue of a saturated or monoor poly-unsaturated hydrocarbon chain; and R is a carbon atom or the residue of a saturated or mono or poly-unsaturated hydrocarbon or secondary alcohol group; and either R or R" may contain further acetylenic linkages; and R and R" comprise, in all, from 7 to 21 carbon atoms.

Typical of these acetylenic acids are octynoic acid and the like; and isanic acid whose structure is reported to be:

CH CH(CH -CEC-'CEC(CH COOH and isanolic acid whose structure is reported to be:

CH (CH CH=CH-CEC- CEC' CH CH (OH) (CH COOH as well as other acids such as may be found in isano oil or boleko or ongokea oil or other acetylenic oil derived from the fruits of related species of plants.

The fatty acids from isano oil contain about 46% of isanic acid and about 44% of isanolic acid along with other fatty acids. For descriptive purposes, this mixture will hereinafter be referred to as isano acid.

Typical examples of the quaternary ammonium compounds which may be used in this invention are the alkyl trimethyl ammonium chlorides, alkyl-benzyl trimethyl ammonium chlorides, alkyl dimethyl benzyl ammonium chlorides, alkyl dimethyl menaphthyl ammonium chlorides, alkyl dimethyl substituted-benzyl ammonium chlorides in which the benzyl radical is substituted with one or more side chains containing from 1 to carbon atoms such, for example, as methyl, dimethyl, ethyl and the like and in which the carbon atoms may all be in the same or different side chains or in which the benzyl radical bears one, two or more halogen atoms such as chlorine or bromine, alkyl pyridinium chlorides, alkyl isoquinolinium chlorides and bromides, alkyl lower-alkyl pyrrolidinium chlorides, alkyl lower-alkyl morpholinium chlorides in all of which the alkyl group may have from 8 to 22 carbon atoms and the lower-alkyl group may have from 1 to 4 carbon atoms and alkyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride in which the alkyl radical may be iso-octyl or nonyl and in which the phenyl radical may, if desired, be substituted by a methyl radical. Various other analogs of these quaternaries may also be employed such, for example, as cetyl dimethyl ethyl am- .monium bromide or oleyl dimethyl ethyl ammonium bromide.

In general, the quaternary ammonium compounds useful in this invention are the higher alkyl quaternary ammonium hydroxides, halides (chlorides and bromides),

3346 265 Patented Sept. 5, 1967 sulfates, methosulfates and the like possessing the following formula:

where R is an alkyl or alkaralkyl radical containing from 8 to 22 carbon atoms or an alkyl phenoxy ethoxy ethyl radical in which R is an alkyl radical containing from 8 to 9 carbon atoms and in which the-phenyl radical may be substituted by a methyl group; R and R are methyl or ethyl radicals or members of a heterocyclic ring system such as pyridine, isoquinoline, pyrrolidine and morpholine; R is a methyl radical or a benzyl group or a substituted-benzyl group such, for example, as a monochlorobenzyl radical or a dichlorobenzyl radical or mixture thereof or a methyl benzyl, dimethyl benzyl, ethyl benzyl, diethyl benzyl, isopropyl benzyl, tertiary butyl benzyl or another benzyl radical containing from 1 to 5 carbon atoms as side chains, either as a single side chain or a multiplicity of side chains including mixtures thereof or a menaphthyl group or hydrogenated menaphthyl group. When R and R are members of a morpholine or pyrrolidine ring, R is a methyl, ethyl, propyl or butyl group. When R and R are members of an unsaturated heterocyclic ring such as pyridine or isoquinoline, R' is the same radical as R. X in the above formula corresponds to a halide radical such as chloride, bromide or iodide or to any other water-soluble anion such as methosulfate.

In general, we prefer to use such quaternary ammonium compounds which have a phenol coefficient of at least with respect to both Staphylococcus aureus and Salmonella typhosa at 20 C. when determined by the standard method given in the Official Methods of Analysis of the Association of Official Agricultural Chemists, ninth edition (1960), pages 63 et seq.

The compounds of this invention may be prepared by mixing aqueous solutions of the quaternary ammonium salts or hydroxides with an aqueous solution of the acetylenic carboxylic acid in question or any of its water-soluble salts.

After thorough mixing, the organic product layer is separated from the aqueous layer (as with a separatory funnel) since two distinct phases are formed. Separation may be facilitated by the addition of an organic solvent immiscible with water. The product layer may be washed with water to remove any residual by-product salt or unreacted materials. The solvent, if any, may be evaporated and the product air or vacuum dried to a paste, wax, oil or solid.

It is not necessary to use an aqueous medium. Any solvent or solvent mixture in which the starting materials are soluble will be satisfactory. Non-aqueous solvents facilitate the separation of by-product inorganic salt and reduce the need for vacuum drying to get an anhydrous product. When a non-aqueous medium is employed, it is usually necessary to add a small amount of water to facilitate ionic reaction.

The product may be used, if desired, without drying since any entrapped water is irrelevant to the microbiological activity of the compounds. In other applications, removal of water may be essential for reasons not related to biological activity.

An alternative method for the preparation of compounds especially applicable to the treatment of fabric, ropes, net, woven and non-woven fabric and reticulated or convoluted materials involves a two-step process. In

0 the first step, the material is passed through a bath contreated material is then passed through a second bath wherein the concentration of quaternary ammonium compound is such that the material pickup will result in an equivalent amount of quaternary ammonium compound reacting with the anionic moiety, depositing the product in the most intimate way on the surface and in the interstices, convolutions and reticulations of the material.

The method of adjustment of solution concentration to achieve the required pickup is well known to those skilled in the art. The order of treatment may be reversed without affecting the biological activity or durability of the product on the material. The products of this invention may be formulated as water dispersions by dissolving them in a water miscible organic solvent such as acetone or methanol and diluting with water or by dissolving them in emulsifiable oils such, for example, as sulfonated castor oil or pine oil and diluting with water. In preparing aqueous dispersions, emulsifying agents such, for example, as ethylene oxide condensates of alkyl phenols may be used with or without organic solvents.

It is surprising that the. compounds of this invention exhibit high microbiological activity despite their relative insolubility in water. Because of their unusual combination of physical and microbiological properties, they can be used to impart laundry-resistant anti-microbial characteristics to textiles. They can also be used as the active agent in antimildew finishes for textiles which are resistant to leaching with water.

Although the compounds have low Water solubility, they are compatible with various organic solvents, plasticizers and high molecular weight compounds. Consequently, they may be incorporated as anti-microbial agents in synthetic resins and plastics. The compounds are compatible with natural and synthetic rubber latices. Therefore, they may be used to prepare bacteriostatic films and molded objects deposited from such latices.

The compounds can be incorporated into cutting and grinding fluids without precipitation. Also, they blend well with non-ionic and anionic surface active agents. In such compositions they retain their microbiological activity.

It will be understood that the properties of the products described herein will vary depending upon the nature of the cationic quaternary ammonium compound used in their preparation as well as the anionic compound reacted therewith.

The chemical, physical and biological properties of the products of our invention make them especially appropriate for the following applications when suitably incorporated in active amounts in an appropriate vehicle, binder, medium or substrate:

(1) Mildewproofing fabric, canvas, ropes, textiles, awnings, sails, tenting and other woven and non-woven reticulated materials.

(2) Paint mildewstats.

(3) Jet plane fuel additive to control growth of microorganisms.

(4) Odor preservative agents for clothes and shoes.

(5) Mildew retardant and odor suppressant for shoes and other leather products.

(6) Topical antiseptics.

(7) Antidandruff agents.

(8) Disinfection agents for hair and gut of man and beast.

(9) Bacteriostatic furniture dressing.

(10) Surface finishes for stone, plaster, tile, cement, brick and other inorganic building materials to retard growth of microorganism, fungi, mold and algae.

(11) Wool preservative.

(12) Plant and tree spray to combat fungi.

(13) Antimycotic agents for soap wrappers.

(14) Self-sanitizing brushes.

(15) Mildewproofing agent in and on plastic and film.

(16) Mildewproofing of cellulosics, cardboard, fibreboard, paper and cordage.

(17) Contact biostat for application to film, waxes and cloth to preserve cheese, meats and vegetables and other food products.

(18) Algal inhibition, especially on surfaces and in solution where low foaming is desirable.

(19) Paper pulp slime control.

(20) Sanitizing agent for rug, carpet, curtains.

(21) Egg preservation.

(22) Adhesive preservation.

(23) Preservation of latex paints.

(24) Preservation of metal-working compounds.

(25) Additives for soap and for both anionic and nonionic detergents in liquid, bar, powder, bead, solution and other forms to impart bacteriostatic and fungi-static properties thereto.

(26) Bacteriostatic agents for household laundry softener-s.

(27) Algastat and bacteriostat in recirculated water for cooling towers, air conditions and humidifiers.

(28) Bacteriostat and algastat for flood waters and brines used in secondary oil recovery.

(29) Fungistat for seed and soil treatment against damping-off.

The microbiological activity of our compounds has been evaluated for microbiological stasis by the Stand ard Tube Dilution Test, the technique for which is common knowledge to those skilled in the art. A Difco Bacto CSMA Broth #0826 was used in the study. This test is used to determine the lowest concentration of microbiologically active compounds which will inhibit the growth of the organism in question. For a wide range of applications, the inhibition of growth rather than outright kill is satisfactory.

Briefly put, the Tube Dilution Test consists in placing 9 cc. of the CSMA Broth in a test tube which is then sterilized in an autoclave. One cc. solution of the microbiologically active compound at an appropriate concentration is added to the test tube which is then inoculated with 0.1 cc. of a twenty-four hour old culture of the organism under study. The test tube is then incubated at 37 C.

for forty-eight hours and observed for bacterial growth.

The same procedure is followed for fungi. In such tests, however, the tubes are incubated for fourteen days at a temperature suitable for optimum fungal growth, usually 25 C.

This invention is illustrated by, but not restricted to, the followingexamples:

Example I Isano oil was saponified with alcoholic potassium hydroxide to produce the potash soap. The excess alkali and the alcohol were removed and the solution was adjusted to 10% concentration by weight.

An aliquot of this solution containing 0.0782 equivalent weights of the soap was agitated vigorously while adding a chemically equivalent amount of a solution of a commercial grade of alkyl dimethyl ethyl-benzyl ammonium chloride (Onyx Chemical Corporations ETC-471 in which the alkyl distribution is 50% C 30% C 17% C 3% C The mixture was transferred to a separatory funnel along with a little benzene and the organic product layer was removed and dried in vacuo. The alkyl dimethyl ethyl-benzyl ammonium salt of isano acid was recovered in theoretical yield as a light brown viscous liquid.

Example II An aliquot of the solution of isano soap of Example I was reacted in the same manner with a chemically equivalent amount of a 10% solution of a commercial grade of alkyl dimethylbenzyl ammonium chloride (Onyx Chemical Corporations ETC-824 in which the alkyl distribution is 60% C 30% C 5% C 5% C On separating and drying, a brown paste of alkyl dimethyl benzyl ammonium salt of isano acid was recovered in 96% of the theoretical yield.

Example lII Similarly, an aliquot of the isano soap solution of Example I was reacted with a chemically equivalent amount of an aqueous-alcohol solution of a commercial grade of alkyl isoquinolinium bromide. The alcohol was removed by evaporation and the residual mixture, with the additin of benzene, was transferred to a separatory funnel. The organic product layer was removed and vacuum dried to yield the theoretical amount of alkyl isoquinolinium salt of isano acid as a dark brown paste.

Example IV A 20% aqueous solution of potassium alpha-octynoate was prepared. An aliquot of this solution containing 0.045 molecular weights of the compound was reacted with a chemically equivalent amount of the alkyl dimethyl ethyl-benzyl ammonium chloride solution of Example I. Benzene was added and the mixture was separated in a separatory funnel. The organic product layer was removed and vacuum dried. The alkyl dimethyl ethyl-benzyl ammonium alpha-octynoate was obtained in the theoretical yield as a viscous orange liquid.

Example V An aliquot of the solution of potassium octynoate of Example IV was reacted in the same manner with a chemically equivalent amount of the solution of alkyl dimethyl benzyl ammonium chloride of Example II. The product, alkyl dimethyl benzyl ammonium alpha-octynoate, was a viscous orange liquid in 99% of the theoretical yield.

Example VI An aliquot of the solution of potassium octynoate of Example IV was reacted with a chemically equivalent amount of the aqueous-alcohol solution of alkyl isoquinolinium bromide of Example III. The alcohol was evaporated off, benzene was added to facilitate phase separation, and the organic product layer was removed and vacuum dried. The theoretical yield of alkyl isoquinolinium alphaoctynoate was obtained as a dark brown viscous liquid.

Example VII When tested by the Standard Tube Dilution Test described above, these products gave the following values for static dilution. (S.a.=Staphyl0c0ccus aureus, S.t. =Salmonella typhosa, A.n.=Aspergillus niger.)

We claim:

1. A quaternary ammonium salt of a carboxylic fatty acid having at least one acetylenic linkage and from 8 to 18 carbon atoms, wherein the quaternary ammonium cation is derived from a quaternary ammonium compound having a phenol coeflicient of at least with respect to both Staphylococcus aureus and Salmonella typhosa at 20 C. and having at least one alkyl having 8 to 22 carbon atoms on the quaternary nitrogen.

2. The alkyl dimethyl ethyl-benzyl ammonium salt of isano acid said alkyl having 8 to 22 carbon atoms.

3. The alkyl dimethyl benzyl ammonium salt of isano acid said alkyl having 8 to 22 carbon atoms.

4. The alkyl isoquinolinium salt of isano acid said alkyl having 8 to 22 carbon atoms.

5. Alkyl dimethyl ethyl-benzyl ammonium alphaoctynoate said alkyl having 8 to 22 carbon atoms.

6. Alkyl dimethyl benzyl ammonium alpha-octynoate said alkyl having 8 to 22 carbon atoms.

7. Alkyl isoquinolinium alpha-octynoate said alkyl having 8 to 22 carbon atoms.

References Cited Schwartz et al.: Surface Active Agents and Detergents, vol. II, Inter-science, 1-958, pp. 222 and 230 relied upon.

ALEX MAZEL, Primary Examiner.

DONALD G. DAUS, Assistant Examiner. 

1. A QUATERNARY AMMONIUM SALT OF A CARBOXYLIC FATTY ACID HAVING AT LEAST ONE ACETYLENIC LINKAGE AND FROM 8 TO 18 CARBON ATOMS, WHEREIN THE QUARTERNARY AMMONIUM CATION IS DERIVED FROM A QUATERNARY AMMONIUM COMPOUND HAVING A PHENOL COEFFICIENT OF AT LEAST 100 WITH RESPECT TO BOTH STAPHYLOCOCCUS AUREUS AND SALMONELLA TYPHOSA AT 20*C. AND HAVING AT LEAST ONE ALKYL HAVING 8 TO 22 CARBON ATOMS ON THE QUATERNARY NITROGEN.
 7. ALKYL ISOQUINOLINIUM ALPHA-OCTYNOATE SAID ALKYL HAVING 8 TO 22 CARBON ATOMS. 